An analytical methodology using automatic thermal desorption and gas chromatography mass spectrometry analysis was optimized and validated for simultaneous determination of a set of components from three different flame retardant chemical classes: polybrominated diphenyl ethers (PBDEs) (PBDE-28, PBDE-47, PBDE-66, PBDE-85, PBDE-99, PBDE-100), organophosphate flame retardants (PFRs) (tributyl phosphate, tripropyl phosphate, tris(2-chloroethyl)phosphate-, tris(1,3-dichloro-2-propyl) phosphate, tris(2-ethylhexyl) phosphate, triphenyl phosphate, tris(2-chloro-1-methylethyl) phosphate and tricresylphosphate), and “novel” brominated flame retardants (NBFRs) (pentabromotoluene, 2,3,4,5,6-pentabromoethylbenzene, (2,3-dibromopropyl) (2,4,6-tribromophenyl) ether, hexabromobenzene, and 2-ethylhexyl 2,3,4,5-tetrabromobenzoate) in air. The methodology is based on low volume active air sampling of gaseous and particulate air fractions on mixed-bed (polydimethylsiloxane (PDMS)/Tenax TA) sorption tubes. The optimized method provides recoveries >88 %; a limit of detection in the range of 6–25 pg m⁻³ for PBDEs, 6–171 pg m⁻³ for PFRs, and 7–41 pg m⁻³ for NBFRs; a linearity greater than 0.996; and a repeatability of less than 10 % for all studied compounds. The optimized method was compared with a standard method using active air sampling on XAD-2 sorbent material, followed by liquid extraction. On the one hand, the PDMS/Tenax TA method shows comparable results at longer sampling time conditions (e.g., indoor air sampling, personal air sampling). On the other hand, at shorter sampling time conditions (e.g., sampling from emission test chambers), the optimized method detects up to three times higher concentrations and identifies more flame retardant compounds compared to the standard method based on XAD-2 loading.

The use of plants and microorganisms to mitigate sediment contaminated by copper was studied in microcosms that mimic the functioning of a stormwater basin (SWB) connected to vineyard watershed. The impact of phytoremediation and bioaugmentation with siderophore-producing bacteria on the fate of Cu was studied in two contrasted (batch vs. semi-continuous) hydraulic regimes. The fate of copper was characterised following its discharge at the outlet of the microcosms, its pore water concentration in the sediment, the assessment of its bioaccessible fraction in the rhizosphere and the measurement of its content in plant tissues. Physico-chemical (pH, redox potential) and biological parameters (total heterotrophic bacteria) were also monitored. As expected, the results showed a clear impact of the hydraulic regime on the redox potential and thus on the pore water concentration of Cu. Copper in pore water was also dependent on the frequency of Cu-polluted water discharges. Repeated bioaugmentation increased the total heterotrophic microflora as well as the Cu bioaccessibility in the rhizosphere and increased the amount of Cu extracted by Phragmites australis by a factor of ~2. Sugar beet pulp, used as a filter to avoid copper flushing, retained 20 % of outcoming Cu and led to an overall retention of Cu higher than 94 % when arranged at the outlet of microcosms. Bioaugmentation clearly improved the phytoextraction rate of Cu in a small-scaled SWB designed to mimic the functioning of a full-size SWB connected to vineyard watershed. HIGHLIGHTS: - Cu phytoextraction in constructed wetlands much depends on the hydraulic regime and on the frequency of Cu-polluted water discharges - Cu phytoextraction increases with time and plant density - Cu bioaccessibility can be increased by bioaugmentation with siderophore-producing bacteria

We investigated the ozonation of the antineoplastic drugs cyclophosphamide (CP), ifosfamide (IF), and 5-fluorouracil (5-FU) and of the vasodilator pentoxifylline (PEN) in distilled water, in pharmaceutical wastewater, and in hospital effluent at pH 5–11. Under an alkaline pH of 11, all of the target compounds rapidly degraded through the attack of hydroxyl radicals, which resulted in their complete removal within 5 min at an ozone supply rate of 3 g O₃/h. Under acidic pH conditions, such as pH 5.6, CP and IF exhibited slower removal rates; however, compounds with unsaturated C-C bonds, such as 5-FU and PEN, were still removed at rapid rates under acidic conditions. Although the parent compounds were removed within minutes, the resulting ozonation byproducts were resistant to further ozonation and possessed increased Microtox acute toxicity. In distilled water, the resulting ozonation products exhibited minimal mineralization but high acute toxicity, whereas in naturally buffered pharmaceutical and hospital effluents, the byproducts were more amenable to removal and detoxification.

Vibrios and other enteric pathogens can be found in wastewater effluents of a healthy population. We assessed the prevalence of three non-cholerae vibrios in wastewater effluents of 14 wastewater treatment plants (WWTP) in Chris Hani and Amathole district municipalities in the Eastern Cape Province of South Africa for a period of 12 months. With the exception of WWTP10 where presumptive vibrios were not detected in summer and spring, presumptive vibrios were detected in all seasons in other WWTP effluents. When a sample of 1,000 presumptive Vibrio isolates taken from across all sampling sites were subjected to molecular confirmation for Vibrio, 668 were confirmed to belong to the genus Vibrio, giving a prevalence rate of 66.8 %. Further, molecular characterisation of 300 confirmed Vibrio isolates revealed that 11.6 % (35) were Vibrio parahaemolyticus, 28.6 % (86) were Vibrio fluvialis and 28 % (84) were Vibrio vulnificus while 31.8 % (95) belonged to other Vibrio spp. not assayed for in this study. Antibiogram profiling of the three Vibrio species showed that V. parahaemolyticus was ≥50 % susceptible to 8 of the test antibiotics and ≥50 % resistant to only 5 of the 13 test antibiotics, while V. vulnificus showed a susceptibility profile of ≥50 % to 7 of the test antibiotics and a resistance profile of ≥50 % to 6 of the 13 test antibiotics. V. fluvialis showed ≥50 % resistance to 8 of the 13 antibiotics used while showing ≥50 % susceptibility to only 4 antibiotics used. All three Vibrio species were susceptible to gentamycin, cefuroxime, meropenem and imipenem. Multiple antibiotic resistance patterns were also evident especially against such antibiotics as tetracyclin, polymixin B, penicillin G, sulfamethazole and erythromycin against which all Vibrio species were resistant. These results indicate a significant threat to public health, more so in the Eastern Cape Province of South Africa which is characterised by widespread poverty, with more than a third of the population directly relying on surface water sources for drinking and daily use.

The presence and composition of soil microbial communities has been shown to have a large impact on plant–plant interactions and consequently plant diversity and composition. The goal of the present study was to evaluate impact of arbuscular mycorrhizal fungi (AMF) and nitrogen-fixing bacteria, which constitutes an essential link between the soil and the plant’s roots. A greenhouse pot experiment was conducted to evaluate the feasibility of using selected microbes to improve Hieracium pilosella and Medicago sativa growth on Zn–Pb-rich site. Results of studies revealed that biomass, the dry mass of shoots and roots, increased significantly when plants were inoculated with mycorrhizal fungi and nitrogen-fixing bacteria. The addition of Azospirillum sp. and Nostoc edaphicum without mycorrhiza suppressed plant growth. Single bacterial inoculation alone does not have a positive effect on M. sativa growth, while co-inoculation with AMF improved plant growth. Plant vitality (expressed by the performance index) was improved by the addition of microbes. However, our results indicated that even dry heat sterilization of the substratum created imbalanced relationships between soil-plant and plants and associated microorganisms. The studies indicated that AMF and N₂-fixers can improve revegetation of heavy metal-rich industrial sites, if the selection of interacting symbionts is properly conducted.

Coastal lagoons are ecosystems highly vulnerable to human impacts because of their situation between terrestrial and marine environment. Mar Menor coastal lagoon is one of the largest lagoons of the Mediterranean Sea, placed in SE Spain and subjected to major human impacts, in particular the mining of metal sulphides. As a consequence, metal concentration in water column and sediments of this ecosystem is usually higher than in other areas. For monitoring ecosystem health, the present study has assessed the ability of Cotylorhiza tuberculata for bioaccumulating metals from sea water. Up to 65 individuals were sampled at 8 different sampling stations during the summer of 2012. Although the concentration values for different elements considered were moderate (Pb: 0.04-29.50 ppm, Zn: 2.27-93.44 ppm, Cd: 0-0.67 ppm, As: 0.56-130.31 ppm) by dry weight of the jellyfish tissues (bell and oral arms combined), bioconcentration levels in relation to seawater metal concentration were extremely high. In any case, the use or disposal of these organisms should consider their metal content because of their potential environmental and health implications.

In this study, the feasibility of an ex situ electrokinetic (EK) process combined with pre-oxidation using hydrogen peroxide (H₂O₂) and pre-washing using ethylenediaminetetraacetic acid (EDTA) was investigated in enhancing the extraction of Cu, Pb, and Zn from actual dredged harbor sediment. H₂O₂ pre-oxidation led to a change in the fractionation of Cu bound to organic matter and the sulfide fraction in the Fe-Mn oxides to the exchangeable fraction, but was not effective at removing metals. In contrast, EDTA pre-washing changed the Fe-Mn oxide-bound fractions of Cu and Pb into easily extractable fractions; 20.1, 27.5, and 32.8 % of Cu, Pb, and Zn were removed, respectively. During EK treatment, metals were transported toward the anode by electromigration of negatively charged complexes such as metal-EDTA and metal-citrate. However, EK treatment did not significantly enhance the removal of metals because metals accumulated near the anodic region with an increase in the exchangeable fraction due to the short EK operating duration and low voltage gradient. Therefore, it is necessary to extend the EK operating duration and/or increase the voltage gradient for effective transportation and removal of metals from sediment.

Scrap Cu-modified cast iron (CMCI) is a potent material for the reduction of 2,4-dinitrotoluene (2,4-DNT) by a surface-mediated reaction. However, the effects of operational parameters and common ions on its reduction and final rate are unknown. Results show that the 2,4-DNT reduction was significantly affected by Cu:Fe mass ratio and the optimum m(Cu:Fe) was 0.25 %. The slight pH-dependent trend of 2,4-DNT reduction by CMCI was observed at pH 3 to 11, and the maximum end product, 2,4-diaminotoluene (2,4-DAT), was generated at pH 7. Dissolved oxygen (DO) in the water reduced the 2,4-DNT degradation and the formation of 2,4-DAT. CMCI effectively treated high concentrations of 2,4-DNT (60 to 150 mg L⁻¹). In addition, varying the concentration of (NH₄)₂SO₄ from 0.001 to 0.1 mol L⁻¹ improved the efficiency of the reduction process. The green rust-like corrosion products (GR-SO₄ ²⁻) were also effective for 2,4-DNT reduction, in which Na₂CO₃ (0.01 to 0.2 mol L⁻¹) significantly inhibited this reduction. The repeated-use efficiency of CMCI was also inhibited. Moreover, 2,4-DNT and its products, such as 4A2NT, 2A4NT, and 2,4-DAT, produced mass imbalance (<35 %). Hydrolysis of Fe³⁺ and CO₃ ²⁻ leading to the generation of Fe(OH)₃ and conversion to FeOOH that precipitated on the surface and strongly adsorbed the products of reduction caused the inhibition of CO₃ ²⁻. The 2,4-DNT reduction by CMCI could be described by pseudo-first-order kinetics. The operational conditions and common ions affected the 2,4-DNT reduction and its products by enhancing the corrosion of iron or accumulating a passive oxide film on the reactivity sites.

The potential phytotoxicity of water extractable toxicants in a typical corn stover biochar, the product of fast pyrolysis, was investigated using an aqueous biochar extract on a soil-less bioassay with tomato plants. The biochar dosage of 0.0–16.0 g beaker⁻¹ resulted in an inverted U-shaped dose-response relationship between biochar doasage and seed germination/seedling growth. This indicated that tomato growth was slightly stimulated by low dosages of biochar and inhibited with higher dosages of biochar. Additionally, antioxidant enzyme activities in the roots and leaves were enhanced at lower dosages, but rapidly decreased with higher dosages of biochar. With the increased dosages of biochar, the malondialdehyde content in the roots and leaves increased, in addition with the observed morphology of necrotic root cells, suggesting that serious damage to tomato seedlings occurred. EC50 of root length inhibition occurred with biochar dosages of 9.2 g beaker⁻¹ (3.5th day) and 16.7 g beaker⁻¹ (11th day) (equivalent to 82.8 and 150.3 t ha⁻¹, respectively), which implied that toxicity to the early growth of tomato can potentially be alleviated as the plant grows.

Impurity of polychlorinated naphthalenes (PCNs) in commercial polychlorinated biphenyl (PCB) formulations has been recognized as a relevant source of PCNs in the environment. Congener-specific analysis of most main PCB formulations has been accomplished previously, excluding the Chinese product. The insulating oil in a stored Chinese electric capacitor containing the major Chinese technical formulation “PCB3” was sampled and tested by isotope dilution technology using high-resolution gas chromatography coupled to high-resolution mass spectrometry (HRGC/HRMS). The detected concentration of PCNs in the Chinese PCB oil sample was 1,307.5 μg/g and therefore significantly higher than that reported in PCB formulations from other countries, as well as that in the transformer oil (ASKAREL Nr 1740) additionally tested in the present study for comparison. Based on the measurement, the total amount of PCNs in Chinese PCB3 oil is estimated to be 7.8 t, which would mean only 0.005 % of global production of PCNs of 150,000 t. The homolog profile is similar to those of PCN in Aroclor 1262 and Clophen A40, where the contributions from hexa-CNs and hepta-CNs are predominant and accounted for similar proportions. The Toxic Equivalent Quantity (TEQ) concentration of dioxin-like PCN congeners is 0.47 μg TEQ/g, with the dominant contributors of CN-73 and CN-66/67. This TEQ content from PCN is higher than that in most other PCB formulations with the exemption of the Russian Sovol formulation. The total TEQ in the historic 6,000 t of the Chinese PCB3 formulation is estimated to be 2.8 kg TEQ.